The pnictogen bond: a quantitative molecular orbital picture
We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A− (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in...
| Authors: | , , , |
|---|---|
| Format: | article |
| Status: | Published version |
| Publication Date: | 2021 |
| Country: | Brasil |
| Institution: | Universidade Federal de Lavras (UFLA) |
| Repository: | Repositório Institucional da UFLA |
| Language: | English |
| OAI Identifier: | oai:repositorio.ufla.br:1/48861 |
| Online Access: | https://repositorio.ufla.br/handle/1/48861 |
| Access Level: | Open access |
| Keyword: | Pnictogen bonds KS-MO Kohn-Sham molecular orbital theory Energy decomposition analysis (EDA) Voronoi deformation density (VDD) |
| Summary: | We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A− (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn–Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO–LUMO interactions between the lone pair of A− and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds. |
|---|